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Abstract:

The present invention provides a novel copolymer of
2,3,3,3-tetrafluoropropene and a non-fluorinated ethylenic hydrocarbon
monomer. The copolymer contains (A) a 2,3,3,3-tetrafluoropropene unit and
(B) a non-fluorinated ethylenic hydrocarbon monomer unit. The
copolymerization ratio (mol % ratio) of (A) and (B) is 99.9:0.1 to
0.1:99.9 and the number average molecular weight of the copolymer is 1000
to 1000000.

Claims:

1. A copolymer of (A) 2,3,3,3-tetrafluoropropene and (B) a
non-fluorinated ethylenic hydrocarbon monomer, the copolymer having a
copolymerization ratio (mol % ratio) of (A) and (B) of 99.9:0.1 to
0.1:99.9, and a number average molecular weight of 1000 to 1000000.

2. The copolymer according to claim 1, wherein the non-fluorinated
ethylenic hydrocarbon monomer (B) is at least one compound selected from
the group consisting of an ether compound containing a carbon-carbon
unsaturated group represented by formula (Ia), an unsaturated carboxylic
acid or a salt or ester thereof represented by formula (Ib), and an
olefin represented by formula (Ic), and each of the compounds may be
processed by at least one of chlorination, bromination, and iodination,
the formulas (Ia) to (Ic) being: R1R2C ═CR3OR4
(Ia) wherein R1, R2, and R3 are the same as or different
from each other, each being H or a C1 to C10 alkyl group which may have a
ring structure, and R4 is a C1 to C20 alkyl group which may have at
least one of a functional group and a ring structure;
R5R6C═CR7OCOR8 (Ib) wherein R5, R6,
and R7 are the same as or different from each other, each being H or
a C1 to C6 alkyl group which may have a ring structure, and R8 is H,
a C1 to C20 alkyl group which may have at least one of a functional group
and a ring structure, or a C6 to C20 aryl group which may contain a
functional group; and R9R10C═CR11R12 (Ic)
wherein R9, R10 and R11 are the same as or different from
each other, each being H or a C1 to C6 alkyl group which may have a ring
structure, and R12 is a C1 to C20 alkyl group which may have at
least one of a functional group and a ring structure, or a C6 to C12 aryl
group which may contain a functional group.

Description:

TECHNICAL FIELD

[0001] The present invention relates to a copolymer of
2,3,3,3-tetrafluoropropene and a non-fluorinated ethylenic hydrocarbon
monomer.

[0002] Conventionally, 2,3,3,3-tetrafluoropropene (HFO-1234yf) is
considered as a relatively stable compound, and used as a compound for a
refrigerant or an electrical heating fluid.

[0003] Since 2,3,3,3-tetrafluoropropene itself has relatively low radical
polymerizability, there are not many documents concerning copolymers of
2,3,3,3-tetrafluoropropene and other monomers, and only some documents
concerning copolymers of 2,3,3,3-tetrafluoropropene and fluoromonomers
(Patent Literatures 1 to 4) are known.

CITATION LIST

Patent Literature

[0004] Patent Literature 1: JP 2004-536171 T

[0005] Patent Literature 2: JP 2003-514955 T

[0006] Patent Literature 3: JP 2003-514956 T

[0007] Patent Literature 4: JP 11-501685 T

SUMMARY OF INVENTION

Technical Problem

[0008] The present invention aims to provide a novel copolymer of
2,3,3,3-tetrafluoropropene and a non-fluorinated ethylenic hydrocarbon
monomer.

Solution to Problem

[0009] The copolymer of 2,3,3,3-tetrafluoropropene and a non-fluorinated
ethylenic hydrocarbon monomer according to the present invention is a
copolymer of (A) 2,3,3,3-tetrafluoropropene and (B) a non-fluorinated
ethylenic hydrocarbon monomer. A copolymerization ratio (molar ratio %)
of (A):(B) is 99.9:0.1 to 0.1:99.9. A number average molecular weight of
the copolymer is 1000 to 1000000.

Advantageous Effects of Invention

[0010] The present invention can provide a novel copolymer of
2,3,3,3-tetrafluoropropene and a non-fluorinated ethylenic hydrocarbon
monomer, using 2,3,3,3-tetrafluoropropene which has not been rarely noted
as a fluoroolefin before.

[0011] The copolymer of the present invention is expected to have various
applications as a substitute for a copolymer of tetrafluoroethylene (TFE)
and an ethylenic hydrocarbon monomer and a copolymer of
chlorotrifluoroethylene (CTFE) and an ethylenic hydrocarbon monomer.

DESCRIPTION OF EMBODIMENTS

[0012] The copolymer of 2,3,3,3-tetrafluoropropene according to the
present invention is a novel copolymer of (A) 2,3,3,3-tetrafluoropropene
and (B) a non-fluorinated ethylenic hydrocarbon monomer, which has not
been disclosed in any documents. The copolymerization ratio (mol % ratio)
of (A):(B) is 99.9:0.1 to 0.1:99.9, and the number average molecular
weight of the copolymer is 1000 to 1000000.

[0013] The 2,3,3,3-tetrafluoropropene is a non-perfluoroolefin represented
by the following formula:

CH2═CF--CF3

and is different from 1,3,3,3-tetrafluoropropene which is a
constitutional isomer and represented by the following formula:

CFH═CH--CF3.

[0014] The 2,3,3,3-tetrafluoropropene itself forms a structural unit which
is amorphous and transparent. Therefore, the copolymer of the present
invention can be either amorphous or crystalline by selecting a
non-fluorinated ethylenic hydrocarbon monomer (B). In addition, the
copolymer of the present invention can be either an elastomer or a
non-elastomer by selecting a proper non-fluorinated ethylenic hydrocarbon
monomer (B).

[0015] The above non-fluorinated ethylenic hydrocarbon monomer (B) is
preferably one or more of monomers represented by the following formulas
(Ia) to (Ic).

[0016] A monomer represented by the formula (Ia) is an ether compound
containing a carbon-carbon unsaturated group represented by the following
formula (Ia):

R1R2C═CR3OR4

[0017] wherein R1, R2, and R3 are the same as or different
from each other, and each are H or a C1 to C10 alkyl group which may have
a ring structure; and R4 is a C1 to C20 alkyl group which may have
at least one of a functional group and a ring structure.

[0018] In the formula (Ia), examples of the ring structure of R1 to
R4 include cyclohexyl groups and aryl groups. The function group for
R4 can be exemplified by hydroxyl groups, carboxyl groups,
carbon-carbon double bonds, and the like. Also, these compounds may be
processed by at least one of chlorination, bromination, and iodination.

[0022] The compounds (Ia-3) containing another unsaturated group are
specifically one or more of benzyl isopropenyl ether, 1,4-butanediol
divinyl ether, and isopropenyl methylether.

[0023] The monomer represented by the formula (Ib) is an unsaturated
carboxylic acid or a salt or an ester thereof, represented by the
following formula (Ib):

R5R6C═CR7OCOR8

[0024] wherein R5, R6, and R7 are the same as or different
from each other, and each are H or a C1 to C6 alkyl group which may have
a ring structure; and R8 is H, a C1 to C20 alkyl group which may
have a functional group and/or a ring structure, or a C6 to C20 aryl
group which may have a functional group.

[0025] In the formula (Ib), examples of the ring structure of the alkyl
group for R5 to R8 include cyclohexyl groups and aryl groups.
The functional group of R8 can be exemplified by hydroxyl groups,
carboxyl groups, carbon-carbon double bonds, and the like. Also, these
compounds may be processed by at least one of chlorination, bromination,
and iodination.

[0026] Examples of the unsaturated carboxylic acid or a salt or an ester
thereof (Ib) include vinyl esters (Ib-1), (meta)acrylic acids and salts
or esters thereof (Ib-2), and other unsaturated carboxylic acids and
salts or esters thereof (Ib-3).

[0029] The other unsaturated carboxylic acids and salts or esters thereof
(Ib-3) are specifically one or more of crotonic acid and undecylenic
acid.

[0030] The monomer represented by the formula (Ic) is an olefin
represented by the following formula (Ic):

R9R10C═CR11R12

[0031] wherein R9, R10, and R11 are the same as or
different from each other, and each are H or a C1 to C6 alkyl group which
may have a ring structure; and R12 is a C1 to C20 alkyl group which
may have a functional group and/or a ring structure, or a C6 to C12 aryl
group which may contain a functional group.

[0032] In the formula (Ic), the ring structure of the alkyl group for
R9 to R12 includes cyclohexyl groups and aryl groups. The
functional group for R12 can be exemplified by hydroxyl groups,
carboxyl groups, and carbon-carbon double bonds. Also, these compounds
may be processed by at least one of chlorination, bromination, and
iodination.

[0034] The copolymer of 2,3,3,3-tetrafluoropropene (A) and a
non-fluorinated ethylenic hydrocarbon monomer (B) can be either a random
copolymer or an alternating copolymer, depending on the kind of the
ethylenic hydrocarbon monomer (B) used.

[0035] The copolymerization ratio (mol % ratio) of
2,3,3,3-tetrafluoropropene (A):non-fluorinated ethylenic hydrocarbon
monomer (B) is 99.9:0.1 to 0.1:99.9 or 99:1 to 1:99, although the ratio
varies depending on the kind and amount of the ethylenic hydrocarbon
monomer (B).

[0036] The number average molecular weight of the copolymer according to
the present invention is in the range of 1000 to 1000000, in the range of
2000 to 900000, or in the range of 3000 to 800000, although it varies
depending on the kind and amount of the ethylenic hydrocarbon monomer
(B); the kind of the solvent; and the kind, amount, and polymerization
temperature of the radical polymerization initiator. In the case where a
solution polymerization is employed, the number average molecular weight
of the copolymer mainly used is not more than 100000, for example.

[0037] The following describes the production method of the copolymer of
the present invention.

[0038] The copolymerization of 2,3,3,3-tetrafluoropropene (A) and a
non-fluorinated ethylenic hydrocarbon monomer (B) of the present
invention can be produced with a radical polymerization initiator via a
radical polymerization, with or without using a polymerization solvent.

[0039] The polymerization method is not limited as long as it proceeds
based on a usual radical reaction, such as block polymerization, solution
polymerization, emulsion polymerization, and suspension polymerization.

[0040] In the present invention, the radical polymerization initiator is
not particularly limited, and it may be either organic or inorganic, and
also may be either fluorinated or non-fluorinated. Also, the
polymerization can be initiated by the methods using heat, light, radial
rays, and the like. One of these may be appropriately selected.

[0041] Examples of usable polymerization initiators include persulfates
such as ammonium persulfate and potassium persulfate (a reducing agent
such as sodium bisulfite, sodium pyrosulfife, cobalt naphthenate, and
dimethylaniline can be further used in combination as needed); redox
initiators formed from an oxidizer (such as ammonium peroxide and
potassium peroxide), a reducing agent (such as sodium sulfite), and a
transition metal salt (such as iron sulfate); diacyl peroxides such as
acetyl peroxide and benzoyl peroxide; dialkoxy carbonyl peroxides such as
isopropoxycarbonyl peroxide and tert-butoxycarbonyl peroxide; ketone
peroxides such as methyl ethyl ketone peroxide and cyclohexanone
peroxide; hydroperoxides such as hydrogen peroxide, tert-butyl
hydroperoxide, and cumene hydroperoxide; dialkyl peroxides such as
di-tert-butyl peroxide and dicumyl peroxide; alkyl peroxy esters such as
tert-butyl peroxyacetate and tert-butyl peroxypivalate; and azo compounds
such as 2,2'-azobisisobutyronitrile,
2,2'-azobis(2,4-dimethylvaleronitrile),
2,2'-azobis(2-methylvaleronitrile),
2,2'-azobis(2-cyclopropylpropionitrile), dimethyl 2,2'-azobisisobutyrate,
2,2'-azobis[2-(hydroxymethyl)propionitrile], and
4,4'-azobis(4-cyanopentanoic acid).

[0042] For the polymerization solvent, water is used in the emulsion
polymerization method, and water, tert-butanol,
1,1,2-trichloro-1,2,2-trifluoroethane,
1,2-dichloro-1,1,2,2-tetrafluoroethane, a mixture of these, or the like
is used in the suspension polymerization method. In the solution
polymerization method, examples of usable polymerization solvents include
esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl
acetate; ketones such as acetone, methyl ethyl ketone, and cyclohexanone;
aliphatic hydrocarbons such as hexane, cyclohexane, octane, nonane,
decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons
such as benzene, toluene, xylene, naphthalene, and solvent naphtha;
alcohols such as methanol, ethanol, tert-butanol, iso- propanol, and
ethylene glycol monoalkyl ethers; cyclic ethers such as tetrahydrofuran,
tetrahydropyran, and dioxane; fluorine solvents such as HCFC225 and
HCFC141b; dimethyl sulfoxide; and mixtures of these.

[0043] The polymerization temperature may be appropriately determined
according to the kinds of the ethylenic hydrocarbon monomer (B) and the
like, and is usually 0° C. to 150° C., and preferably
5° C. to 95° C. in any polymerization methods. The
polymerization pressure is usually 0.1 to 10 MPaG (1 to 100
kgf/cm2G) in any polymerization methods.

[0044] Since the copolymer of the present invention contains the
2,3,3,3-tetrafluoropropene (A) units, the copolymer has excellent
properties in transparency, weather resistance, chemical resistance, and
solvent resistance. Therefore, the copolymer can be expected to have
various applications as a substitute for a copolymer of
tetrafluoroethylene (TFE) and an ethylenic hydrocarbon monomer, and a
copolymer of chlorotrifluoroethylene (CTFE) and an ethylenic hydrocarbon
monomer.

EXAMPLES

[0045] Hereinafter, the present invention will be described in more detail
based on examples. However, the examples are not intended to limit the
scope of the present invention.

[0046] The following are the devices used for evaluation of the physical
properties and the measurement conditions.

[0054] Measurement condition: Tetrahydrofuran is used as an eluate, and a
polystylene with a known molecular weight is used as a standard sample
for molecular weight determination.

(4) Glass Transition Temperature and Crystalline Melting Point

[0055] In accordance with ASTM E1356-98, a glass transition temperature
and a crystalline melting point are determined from heat absorption in a
second run by a midpoint method, using a DSC measurement device produced
by Mettler Toledo K. K.

Measurement Conditions

[0056] Rate of temperature rise: 20° C./min

[0057] Amount of sample: 10 mg

[0058] Heat cycle: -100° C. to 150° C., heating, cooling,
and heating

Example 1

[0059] To a 300-mL stainless steel autoclave were added butyl acetate (80
g), hydroxybutyl vinyl ether (HBVE, 20.3 g), and Perbutyl PV (a peroxide
radical polymerization initiator produced by NOF Corporation, 0.21 g).
The air in the autoclave was substituted with nitrogen and then cooled to
5° C. Subsequently, 2,3,3,3-tetrafluoropropene (30 g) was added to
the autoclave. The inside of the autoclave was heated to 60° C.
with stirring, whereby the reaction was initiated. The reaction was
performed for 7 hours with keeping the temperature in the autoclave at
60° C. Then temperature and pressure in the autoclave were brought
to the ambient temperature and pressure to terminate the
copolymerization, whereby 128 g of a butyl acetate solution of a
fluorocopolymer (solid content concentration: 31 mass %) was produced.
The produced copolymer had a glass transition temperature of 14°
C., a number average molecular weight (Mn) of 7300, and a fluorine
content of 62 mass %, and the copolymerization ratio (mol % ratio)
thereof was 2,3,3,3-tetrafluoropropene/HBVE=62/38. In addition, the
copolymer was amorphous with no crystalline melting point observed.

[0062] To a 300-mL stainless steel autoclave were added butyl acetate (80
g), ethyl vinyl ether (EVE, 12.6 g), and Perbutyl PV (0.21 g). The air in
the autoclave was substituted with nitrogen and then cooled to 5°
C. Subsequently, 2,3,3,3-tetrafluoropropene (30 g) was added to the
autoclave. The inside of the autoclave was heated to 60° C. with
stirring, whereby the reaction was initiated. The reaction was performed
for 8 hours with keeping the temperature in the autoclave at 60°
C. Then temperature and pressure in the autoclave were brought to the
ambient temperature and pressure to terminate the polymerization, whereby
120 g of a butyl acetate solution of a fluorocopolymer (solid content
concentration: 23.9 mass %) was produced. The produced copolymer had a
glass transition temperature of -1° C., a number average molecular
weight (Mn) of 3100, and a fluorine content of 72 mass %, and the
copolymerization ratio (mol % ratio) thereof was
2,3,3,3-tetrafluoropropene/EVE=62/38. In addition, the copolymer was
amorphous with no crystalline melting point observed.

[0065] To a 300-mL stainless steel autoclave were added butyl acetate (80
g), vinyl acetate (15.1 g), and Perbutyl PV (0.21 g). The air in the
autoclave was substituted with nitrogen and then cooled to 5° C.
Subsequently, 2,3,3,3-tetrafluoropropene (30 g) was added to the
autoclave. The inside of the autoclave was heated to 60° C. with
stirring, whereby the reaction was initiated. The reaction was performed
for 15 hours with keeping the temperature in the autoclave at 60°
C. Then temperature and pressure in the autoclave were brought to the
ambient temperature and pressure to terminate the polymerization, whereby
122 g of a butyl acetate solution of a fluorocopolymer (solid content
concentration: 27.6 mass %) was produced. The produced copolymer had a
glass transition temperature of 21.5° C., a number average
molecular weight (Mn) of 29000, and a fluorine content of 56 mass %, and
the copolymerization ratio (mol % ratio) thereof was
2,3,3,3-tetrafluoropropene/vinyl acetate=51/49. In addition, the
copolymer was amorphous with no crystalline melting point observed.

[0068] To a 300-mL stainless steel autoclave were added butyl acetate (80
g), 1-decene (15.2 g), and Perbutyl PV (a peroxide radical polymerization
initiator produced by NOF Corporation, 0.21 g). The air in the autoclave
was substituted with nitrogen and then cooled to 5° C.
Subsequently, 2,3,3,3-tetrafluoropropene (18.6 g) was added to the
autoclave. The inside of the autoclave was heated to 60° C. with
stirring, whereby the reaction was initiated. After the reaction was
performed for 16 hours with keeping the temperature in the autoclave at
60° C., temperature and pressure in the autoclave were brought to
the ambient temperature and pressure to terminate the polymerization.
Thereby, 105.9 g of a butyl acetate solvent of a
2,3,3,3-tetrafluoropropene/1-decene copolymer (solid content
concentration: 1.5 mass %) was produced.

Example 5

[0069] To a 300-mL stainless steel autoclave were added butyl acetate (80
g), methyl methacrylate (17.5 g), and Perbutyl PV (0.21 g). The air in
the autoclave was substituted with nitrogen and then cooled to 5°
C. Subsequently, 2,3,3,3-tetrafluoropropene (30 g) was added to the
autoclave. The inside of the autoclave was heated to 60° C. with
stirring, whereby the reaction was initiated. After the reaction was
performed for 14 hours with keeping the temperature in the autoclave at
60° C., temperature and pressure in the autoclave were brought to
the ambient temperature and pressure to terminate the polymerization.
Thereby, 115.71 g of a butyl acetate solution of a fluorocopolymer (solid
content concentration: 12.2 mass %) was produced. The produced copolymer
had a glass transition temperature of 97° C., a number average
molecular weight (Mn) of 19000, a weight average molecular weight (Mw) of
35000, and a fluorine content of 1.7 mass %, and the copolymerization
ratio (mol % ratio) thereof was 2,3,3,3-tetrafluoropropene/methyl
methacrylate=2/98.

Patent applications by Katsuhiko Imoto, Settsu-Shi JP

Patent applications by Yuji Imahori, Settsu-Shi JP

Patent applications by DAIKIN INDUSTRIES LTD.

Patent applications in class Two or more fluorine atoms, e.g., vinylidene fluoride, etc.

Patent applications in all subclasses Two or more fluorine atoms, e.g., vinylidene fluoride, etc.